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Photocatalysis techniques for converting CO 2 into valuable chemicals driven by solar irradiation has drawn increasing attention. While many photocatalysts often generate by-products that pose challenges for the subsequent synthesis of more complex products. Therefore, designing catalysts with both high selectivity and activity has become a critical issue. Our study reveals that the formation of dual-active-center in Co doping LiNbO 3 (Co-LN) photocatalyst greatly improves the yield and selectivity of CO in photoreduction of CO 2 in pure water at room temperature without requiring additional sacrificial agents. The extended X-ray absorption fine structure spectroscopy together with some in-situ measurement techniques and theoretical calculations reveal that the dual-active-center of oxygen vacancy and Co-dopant stabilizes the *CO 2 and *CO intermediates, respectively, which regulates the rate-limiting step and facilitates the high activity and selectivity. This research will stimulate in-depth research on the use of efficient niobate materials for the photocatalytic conversion of CO 2. [Display omitted] • Co doping greatly enhances the concentration of oxygen vacancy. • The Co-LN shows considerable CO yield and 100 % selectivity without any sacrificial agents and photosensitizers in pure water. • The synergistic effect of Co and oxygen vacancy promotes the adsorption of CO 2 and reduces the energy barrier. • This research will stimulate in-depth research on the use of new and efficient niobate for photocatalytic conversion of CO 2. [ABSTRACT FROM AUTHOR]

Photocatalysis suffers from rapid recombination of photoexcited charge carriers and limited active sites for the catalytic reactions, resulting in unsatisfactory performances that are far from practical application. Single metal atom catalysts not only increase the number of active sites due to the maximum atom‐utilization efficiency, but also enhance the intrinsic activity of each active site because of their unique geometric and electronic features. Furthermore, single metal atom catalysts provide a platform for photocatalysis research on the atomic level. This review discusses the unique characteristics, including geometric and electronic properties, of single metal atom catalysts, summarizes their synthesis strategies, and reviews their most recent development in photocatalysis. Finally, the challenges of single metal catalysts for both fundamental research and practical application are highlighted. [ABSTRACT FROM AUTHOR]